JP5295564B2 - Dense mixed titanium lithium oxide powdery compound, method for producing the compound, and electrode comprising the compound - Google Patents

Dense mixed titanium lithium oxide powdery compound, method for producing the compound, and electrode comprising the compound Download PDF

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JP5295564B2
JP5295564B2 JP2007528917A JP2007528917A JP5295564B2 JP 5295564 B2 JP5295564 B2 JP 5295564B2 JP 2007528917 A JP2007528917 A JP 2007528917A JP 2007528917 A JP2007528917 A JP 2007528917A JP 5295564 B2 JP5295564 B2 JP 5295564B2
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キャロル、ブルボン
セブリンヌ、ジュアノー
フレデリック、ル、クラ
エレーヌ、リニエ
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コミサリア ア レネルジー アトミック エ オ ゼネルジー アルテルナティブCommissariat A L’Energie Atomique Et Aux Energies Alternatives
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Abstract

A powdery compound selected from the group consisting of Li4Ti5O12 and its derivatives selected from the group consisting of Li4−xMxTi5O12 and Li4Ti5−yNyO12 (x and y between 0 and 0.2, M and N selected from the group consisting of Na, K, Mg, Nb, Al, Ni , Co, Zr, Cr, Mn, Fe, Cu, Zn, Si and Mo), used as active material of an electrode for a lithium storage battery, consists of unitary particles having a diameter not greater than 1 μm and 10-50% volume agglomerated particles having a diameter not greater than 100 μm wherein the agglomerated particles formed by agglomeration of said unitary particles. The method for producing such a compound preferably consists in grinding the synthesized oxide for a duration comprised between 24 hours and 48 hours in a planetary mill and in then performing thermal treatment at a temperature comprised between 450° C. and 600° C.

Description

Background of the Invention

  The present invention relates to mixed powders of titanium lithium oxide, methods for producing such compounds and electrodes for electrochemical energy storage devices comprising such compounds.

  The electrochemical energy storage device comprises, inter alia, an energy storage device that operates on lithium. In that case, such a device comprises at least one electrode comprising lithium. More specifically, a device called a lithium storage battery comprises two electrodes that contain lithium. There are also hybrid devices that comprise only a single electrode containing lithium.

  Lithium storage batteries or lithium batteries tend to replace rechargeable nickel-cadmium (Ni-Cd) or nickel-hydride (Ni-MH) storage batteries as independent energy sources, especially in portable products. It is getting stronger and stronger. In fact, lithium storage batteries exhibit performance superior to that of Ni-Cd and Ni-MH storage batteries, and in particular have a higher mass energy density.

Lithium storage batteries are based on the principle of Li + ion insertion and desorption at the positive electrode. The positive electrode actually comprises at least one material that can insert a certain number of Li + cations into its structure. For example, materials used as positive electrode active materials are typically TiS 2 , NbSe 3 , V 2 O 5 , LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiV 3 O 8, and more recently LiFePO 4. 4 is selected. The negative electrode of such a lithium storage battery can be a Li + ion generator and can also include an active lithium intercalation material. Thus, the negative electrode active material generally comprises metallic lithium, a lithium alloy, a nanometric mixture of lithium alloys in lithium oxide, lithium and transition metal nitrides, lithium intercalation or intercalation materials such as lithium and titanium. , Carbon in the form of graphite or spinel structural material Li 1 + x Ti (2-y) / 4 O 4 , where x and y are each 0 to 1 to achieve the active material of the negative electrode.

JP 2003-137547 proposes the use of mixed titanium and lithium oxide Li 4 Ti 5 O 12 as active materials for the positive or negative electrode of a secondary lithium storage battery. This Li 4 Ti 5 O 12 oxide is obtained by mixing the precursors in water, then drying the mixture and then heat treating at a temperature of 700 ° C. to 1000 ° C. The mixture is then crushed to form a compound in the form of a powder having a uniform particle size distribution with an average particle size of 0.5-1.5 μm and a maximum diameter of 25 μm. Thus, the Li 4 Ti 5 O 12 oxide produced in can produce a lithium storage battery showing good power performance, but its density does not exceed 0.85 g / ml. This low density leads to the disadvantage that the electrode is bulky and thus the size of the lithium storage battery is large.

In US Patent Application No. 2003/0017104, Li 4 Ti 5 O 12 oxide is synthesized to obtain an adjusted uniform fine particle diameter of 5 nm to 2000 nm and a specific surface area of 1 to 400 m 2 / g. This oxide synthesis involves grinding the mixed titanium and lithium oxide source in an aqueous solution to obtain a predetermined particle size smaller than the particle size required for the final oxide. The solution is then spray dried and reprocessed thermally, for example at a temperature of 250 ° C to 900 ° C. By this drying and heat treatment step, the diameter of the fine particles can be increased, and a narrow particle size distribution and an adjusted specific surface area can be obtained. After the heat treatment step, the product is redispersed in water and the aggregates formed during the heat treatment are separated.

Object of the invention

  The object of the present invention is to obtain a mixed titanium lithium oxide powdery compound having a high density, good electrochemical performance, preferably low levels of impurities and structural defects.

  According to the invention, this object is achieved by the claims.

  More specifically, the object is that the powdered compound is formed by microparticles having a diameter of 1 μm or less and at least 10% by volume of granules formed by agglomeration of the microparticles and having a diameter of 100 μm or less. This is achieved by the fact that

   In the first aspect of the present invention, the ratio of the granular material formed by aggregation is 30 to 50% by volume with respect to the total volume of the compound.

  In the second aspect of the present invention, the diameter of the fine particles is 0.1 μm to 0.5 μm.

  Another object of the present invention is to provide a method for producing a powdered compound of mixed lithium lithium oxide that can be easily carried out and can obtain a dense compound without impairing the electrochemical performance of the compound. It is to be.

According to the invention, this object is at least the following continuous process: a process for synthesizing powdered mixed lithium lithium oxide,
The oxide is pulverized in a planetary mill for 24 to 48 hours, fine particles having a diameter of 1 μm or less, and at least 10% by volume of granules having a diameter of 100 μm or less formed by aggregation of the fine particles; Forming step,
-Achieved by a method comprising a heat treatment at a temperature of 450C to 600C.

  In one embodiment of the present invention, the step of pulverizing the oxide is performed with an organic solvent of less than 5% by volume based on the total volume of the mixed titanium lithium oxide.

In another aspect of the present invention, the step of synthesizing the mixed titanium lithium oxide comprises at least pulverizing the mixed titanium lithium oxide precursor for 1 to 2 hours.
-Heat treating at a temperature reaching 900 ° C.

  Another object of the present invention is to obtain an electrode comprising a powdered compound of titanium lithium oxide mixed, having an excellent power performance and a small volume electrochemical energy storage device. It is.

  According to the present invention, the object is that the electrode comprises at least a powdered compound of titanium lithium oxide mixed, the powdered compound being composed of fine particles having a diameter of 1 μm or less, and by aggregation of the fine particles. This is achieved by having at least 10% by volume of the granules formed have a diameter of 100 μm or less.

  Other advantages and features will become apparent from the description of particular embodiments of the invention, which will now be described by way of non-limiting example only with reference to the accompanying drawings.

Description of special embodiments

According to the present invention, the mixed powdery compound of titanium lithium oxide, more specifically the compound having the empirical formula Li 4 Ti 5 O 12 or the derivative of Li 4 Ti 5 O 12 is
A first particle size group formed by unitary particles of Li 4 Ti 5 O 12 or a derivative of Li 4 Ti 5 O 12 , and a specific number of the single particles formed by aggregation It consists of the 2nd particle size group formed with the granular material.

Among the derivatives of Li 4 Ti 5 O 12 , the powdered compound can be selected from, for example, Li (4-x) M x Ti 5 O 12 and Li 4 Ti (5-y) N y O 12 , Where x and y are each 0 to 0.2, and M and N are Na, K, Mg, Nb, Al, Ni, Co, Zr, Cr, Mn, Fe, Cu, Zn, Si and It is a chemical element selected from Mo.

  A single fine particle means a fine particle not having a diameter of 1 μm or less, preferably 0.1 to 0.5 μm, not bound to each other. Granules formed by agglomeration of single fine particles are also called agglomerated fine particles and have a diameter of 100 μm or less.

Furthermore, the ratio of the granular material formed by aggregation is at least 10% by volume with respect to the total volume of the powdery compound. Preferably, the proportion of the granulate is 30-50% by volume with respect to the total volume of the compound. The pulverulent compound of the empirical formula Li 4 Ti 5 O 12 is composed of, for example, 60% by volume of single particles and 40% by volume of the particles so that each granule has a diameter much larger than the diameter of each particle. It can comprise a granulate formed by agglomeration.

With such a particle size distribution, a mixed titanium lithium oxide compound having a high packing density of preferably 1 g / cm 3 or more can be obtained. Further, BET specific surface area measured by (Brunauer-Emmett-Teller) technique is preferably 5 to 30 m 2 / g, more preferably from about 10 m 2 / g.

Such pulverulent compounds can be obtained from precursors or reactants by any kind of known means, a kind of preliminary synthsis of mixed titanium lithium oxide Li 4 Ti 5 O 12 or derivatives thereof. It is preferable to obtain by performing. For example, Li 4 Ti 5 O 12 is formed by reacting lithium carbonate (Li 2 CO 3 ) with titanium or a rutile mixed oxide (TiO 2 ) by the following reaction by a dry production method.
2.06Li 2 CO 3 + 5TiO 2 → Li 4 Ti 5 O 12 + 2.06CO 2 + 0.06Li 2 O

A slight excess of Li 2 CO 3 is blended to suppress evaporation of the reactant during the reaction.

The synthesis is performed in a planetary mill by thoroughly mixing the reactants with a solvent, such as heptane, for 1-2 hours. The mixture is then dried, placed in an alumina crucible and heat treated at a temperature reaching 900 ° C. The heat treatment is preferably carried out slowly for 10 to 20 hours, for example, at a temperature rising rate of 1 ° C. to 3 ° C. per minute with two temperature holding periods of 450 ° C. to 550 ° C. and 650 ° C. to 700 ° C. The mix is then further heat treated at a cooling rate of 0.5 ° C. to 2 ° C. per minute with intermediate milling if necessary. Such a synthesis process yields pure and powdered mixed titanium lithium oxide Li 4 Ti 5 O 12 having an average diameter generally exceeding 1 μm and having a narrow particle size distribution.

To obtain derivatives of Li 4 Ti 5 O 12 , such as Li (4-x) M x Ti 5 O 12 and Li 4 Ti (5-y) N y O 12 , element M or element N The precursor is added to the oxide reactant.

  The powdered mixed lithium lithium oxide is then placed in a planetary mill, also called a centrifugal mill, and subjected to strong grinding for 24-48 hours. For example, using a 250 ml agate bowl designed to rotate at a rotational speed of 400 rpm and comprising 10 balls with a diameter of 20 mm, 100 g of powdered compound is crushed. The grinding is preferably carried out with less than 5% by volume of an organic solvent selected from, for example, heptane and hexane. In particular, this pulverization is performed in a dry state, that is, without using a solvent that promotes the aggregation of single fine particles.

During this strong pulverization step, the size of the Li 4 Ti 5 O 12 fine particles is reduced, and fine particles having a diameter of 1 μm or less are obtained. Further, specific particles are pressed against the edge of the bowl by the balls, thereby forming a cluster of bonded particles when grinding is completed. These clusters then form granules with a maximum diameter of 100 μm in a proportion of at least 10% by volume with respect to the total volume of the compound.

  Thus, the intensive grinding process yields a powdered compound comprising two different particle size groups, but this intensive grinding process is detrimental to lithium battery electrode applications and more particularly to the electrochemical performance of the compound. Some stresses and structural defects are induced in the powdery compound.

  In order to overcome this drawback, the powdered compound is placed in a quartz tube in an inert atmosphere, for example argon. The quartz tube is then sealed and placed in a furnace preheated to a temperature lower than the temperature of heat treatment when the oxide is synthesized for 10 to 30 minutes. More specifically, the furnace temperature is 450 ° C. to 600 ° C., preferably 500 ° C. This heat treatment process eliminates stresses and defects generated in the titanium lithium oxide crystals mixed during the strong grinding process.

Such a production method is easy to carry out, and a dense powdery compound can be obtained without impairing its electrochemical performance. In fact, by such a method, a compound exhibiting a special particle size distribution in which the portion of the volume occupied by the Li 4 Ti 5 O 12 crystal is reduced by agglomeration, thereby increasing the packing density of the compound. Can be obtained. In addition, the compound has an electrochemical equivalent to the electrochemical performance of the Li 4 Ti 5 O 12 compound with a homogeneous and narrow particle size distribution because the granules formed by aggregation remain lithium-insertable. Show performance.

  Furthermore, the powdery compound advantageously has an impurity ratio of 1% or less per mole of titanium and a low structural defect and stress ratio, thereby improving the electrochemical performance.

In a special embodiment, Li 4 Ti 5 O 12 oxide is synthesized by mixing 201.5 grams of TiO 2 with 76.11 grams of Li 2 CO 3 with heptane for 1-2 hours on a planetary mill. . The resulting mixture is then dried at 60 ° C. for 12 hours and then placed in a 250 ml alumina crucible. Next, this crucible is put into a muffle furnace, and an oxide is synthesized by heat treatment including the following steps.
-Increase the first temperature at a processing rate of 2 ° C per minute, hold for 15 hours after reaching the first constant temperature range of 500 ° C,
A second temperature increase is performed at a processing rate of 2 ° C. per minute, and after reaching the second constant temperature range of 680 ° C., hold for 15 hours;
A third temperature increase is performed at a processing rate of 2 ° C. per minute and is held for 5 hours after reaching the final constant temperature range of 900 ° C.

  The resulting powder is then homogenized in heptane for 1 hour in a planetary mill followed by additional heat treatment. In this additional heat treatment, the temperature is raised to 900 ° C. at a treatment rate of 5 ° C. per minute, then the temperature is held at 900 ° C. for 5 hours, and then lowered to a normal temperature at 25 ° C. per minute.

The 190 grams of Li 4 Ti 5 O 12 obtained in this way is then mixed on a planetary mill for a period of 24 to 48 hours, at the maximum speed transmitted from the mill, in particular at 400 rpm. The 20-30 grams of the mixture is then placed in an inert atmosphere in a quartz tube and heat treated for 15 minutes in a furnace preheated to a temperature of 500 ° C.

The powdery compound thus obtained has a packing density of 1.4 g / cm 3 . From the laser granulometry analysis shown in FIG. 1, it can be seen that this compound is mainly formed from two types of fine particle groups A and B. Group A has a narrow particle size distribution with a fine particle size of 0.1 μm to 1 μm and an average fine particle size of about 0.5 μm, whereas Group B has a wide particle size distribution with a particle size of 1 μm to 100 μm. Moreover, the proportions of groups A and B are about 60% and 40% by volume, respectively. By observing with a scanning electron microscope (SEM) shown in the image of FIG. 2, a special form including fine particles 1 and 2 having different sizes of the powdery compound is also confirmed. The fine particles 1 represent the group A fine particles having a diameter of less than 1 μm, while the fine particles 2 represent the larger granular group B. In addition, the image of FIG. 2 shows that the granular material 2 is formed by clusters of fine particles 1 obtained by aggregation.

Depending on the density of the powdery compound thus obtained, an electrode for use in a high-performance electrochemical energy storage device having a small volume, such as a lithium battery, can be formed. The electrode can be formed, for example, by a nano-dispersion comprising at least a mixed powdered titanium lithium oxide powder together with at least one conductive additive and / or polymer binder. In a special embodiment, the electrode is formed on an aluminum current collector with a dense oxide Li 4 Ti 5 O 12 80% by weight, a conductive additive such as carbon black, 8% by weight, and a polymer organic binder. Produced by depositing a mixture comprising 12% by weight. The polymeric organic binder is selected from, for example, polyether, polyester or methyl methacrylate, acrylonitrile, or vinylidene fluoride polymers.

Such an electrode can be used, for example, as a positive electrode in a lithium storage battery, the battery further comprising a negative electrode made from a separator impregnated with metallic lithium and a liquid electrolyte. The liquid electrolyte can be formed from any type of liquid electrolyte known in the field of lithium storage batteries. For example, the electrolyte may be a lithium salt such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 or an aprotic solvent such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and / or methyl ethyl carbonate. LiCH 3 SO 3 .

A lithium storage battery comprising a positive electrode having a powdered compound Li 4 Ti 5 O 12 as a base, a metallic lithium electrode and a separator impregnated with a liquid electrolyte containing LiPF 6 1M in a propylene carbonate solution was tested. The positive electrode comprises an aluminum current collector, on which a mixture comprising 80% by weight of dense Li 4 Ti 5 O 12, 8% by weight of carbon black, and 12% by weight of polyvinylidene hexafluoride Is deposited. In this case, Li 4 Ti 5 O 12 acts as a material that inserts and desorbs lithium coming from the negative electrode, and can exchange three lithium ions. Have

FIG. 3 shows the relationship between the capacity of a lithium storage battery and the number of cycles in terms of C / N under various current conditions, where N is the charge / discharge of the battery, ie Li 4 Ti 5. It is the number of hours per lithium insertion and desorption in the O 12 material. Therefore,
-The smaller N, the stronger the current and the faster the charge and discharge cycle,
-In weak conditions, e.g. C / 10, the battery reaches a nominal capacity of 160 mAh / g;
-The behavior of the lithium battery is stable for all current conditions (C / 10-20C);
It can be seen that even in strong conditions, for example 20 C, the capacity of the lithium storage battery is still about 60 mAh / g, ie 40% of the nominal capacity obtained under weak conditions.

  Therefore, this storage battery exhibits excellent electrochemical properties, more specifically, high capacity at both low conditions (C / 10) and high conditions (20C). In addition, the nominal capacity is high, i.e. the capacity per gram of active material is high and the powdery compound has a high density, so the capacity per volume is also high.

The present invention is not limited to the above embodiments. For example, the powdered compound can also be used as an active material in a negative electrode for a lithium storage battery. In this case, the positive electrode comprises any kind of active material known in the field of lithium storage batteries. The positive electrode can comprise, for example, LiFePO 4 , LiMn 2 O 4 or LiNi 0.5 Mn 1.5 O 4 . For example, a lithium battery includes a negative electrode containing Li 4 Ti 5 O 12 of the present invention, a positive electrode containing Li 4 Ti 5 O 12 , and a separator impregnated with a liquid electrolyte formed of LiPF 6 1M with a propylene carbonate solution. Can comprise. Then these positive and negative electrodes, the storage capacity of the active material of the negative electrode to take advantage 100%, 3LiFePO 4 is arranged to face the 1Li 4 Ti 5 O 12. Such a storage battery operates at a potential of 1.9V with respect to lithium.

  In the hybrid electrochemical energy storage device, the second electrode, that is, the positive electrode is formed of, for example, carbon black having a high specific surface area.

The particle size distribution of the powdery compound of this invention obtained by the laser particle size measuring method is shown. The photograph of the powdery compound of this invention obtained with the scanning electron microscope is shown. The relationship between the capacity and cycle number of a lithium storage battery comprising a positive electrode baseed with a powdered compound of the present invention is shown under various current conditions.

Claims (14)

  1. -A first group of non-aggregated titanium lithium oxide microparticles (1) having a diameter of 1 µm or less;
    From 1μm formed by agglomeration of fine particles of a plurality of the lithium titanium oxide having a diameter of less than (1), and a second group consisting of grain-shaped body each that have a diameter of less than 100 [mu] m (2) - A powdered compound of mixed titanium lithium oxide , wherein the second group is contained in an amount of 10 to 50% by volume based on the total volume of the powdered compound,
    The mixed titanium lithium oxide powdery compound, wherein the mixed titanium lithium oxide powdery compound has a packing density of 1 g / cm 3 or more .
  2.   2. The compound according to claim 1, wherein a ratio of the granule (2) formed by aggregation is 30 to 50% by volume with respect to a total volume of the compound.
  3.   The compound according to claim 1 or 2, wherein the fine particles (1) have a diameter of 0.1 µm to 0.5 µm.
  4.   The compound as described in any one of Claims 1-3 whose ratio of the impurity of the said compound is 1% or less per mol of titanium.
  5. The compound according to claim 1, wherein the empirical formula of the compound is selected from Li 4 Ti 5 O 12 and derivatives thereof.
  6. The Li 4 Ti 5 O 12 derivative is selected from Li (4-x) M x Ti 5 O 12 and Li 4 Ti (5-y) N y O 12 , where x and y are each 0 to 0.2 and M and N are chemical elements selected from Na, K, Mg, Nb, Al, Ni, Co, Zr, Cr, Mn, Fe, Cu, Zn, Si and Mo, respectively. 6. A compound according to claim 5.
  7. Specific a surface area of 5 to 30 m 2 / g, a compound according to any one of claims 1-6.
  8. A method for producing a powdered compound of mixed titanium lithium oxide according to any one of claims 1 to 7 , comprising at least the following continuous steps:-Powdered mixed lithium lithium A step of synthesizing an oxide;
    The oxide is pulverized in a planetary mill for 24 to 48 hours and formed by agglomeration of fine particles (1) having a diameter of 1 μm or less and fine particles (1) and having a diameter of 100 μm or less, at least 10 A method comprising the steps of: forming a volume% granulate (2); and-heat treating at a temperature of 450C to 600C.
  9. The method according to claim 8 , wherein the step of grinding the oxide is performed with an organic solvent of less than 5% by volume based on the total volume of the mixed titanium lithium oxide.
  10. The step of synthesizing the mixed titanium lithium oxide includes at least pulverizing the mixed titanium lithium oxide precursor for 1 to 2 hours;
    The method according to claim 8 or 9 , comprising the step of heat treatment at a temperature reaching 900 ° C.
  11. The method of claim 10 , wherein the mixed titanium lithium oxide precursor is TiO 2 and Li 2 CO 3 .
  12. During the pulverization process, precursors of chemical elements selected from Na, K, Mg, Nb, Al, Ni, Co, Zr, Cr, Mn, Fe, Cu, Zn, Si and Mo were mixed. The method according to claim 10 or 11 , which is added to a precursor of titanium lithium oxide.
  13. An electrode for an electrochemical energy storage device comprising at least the powdery compound of the mixed titanium lithium oxide according to any one of claims 1 to 7 .
  14. 14. Electrode according to claim 13 , consisting of a nano-dispersion of the powdered compound with at least one conductive additive and / or polymer binder.
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